Field of Invention
[0001] This invention relates to a pneumatic tire having an air retention innerliner.
Background of the Invention
[0002] The inner surface of pneumatic rubber tires is typically comprised of a rubbery,
elastomeric composition designed to prevent or retard the permeation of air and moisture
into the carcass from the tire's air chamber. The portion of the tire containing such
inner surface is often referred to as an innerliner. Innerliners have also been used
for many years in tubeless pneumatic vehicle tires to retard or prevent the escape
of air used to inflate the tire, thereby maintaining tire presssure. Rubbers which
are relatively impermeable to air are often used as a major portion of said innerliners
and can include butyl rubber and halobutyl rubbers. U.S. Patent 3,808,177 discloses
other polymers which may also be relatively impermeable. Further prior art references
of interest are DE-A-2 601 535, US-A-4 279 284 and US-A-2 996 095.
[0003] The innerliner is normally prepared by conventional calendering or milling techniques
to form a strip of uncured compounded rubber, which is sometimes referred to as a
gum strip. Typically, the gum strip is the first element of the tire to be applied
to a tire building drum, over and around which the remainder of the tire is built.
When the tire is cured, such innerliner becomes an integral, co-cured, part of the
tire.
[0004] The preparation of a gum strip composed entirely of compounded chlorobutyl or bromobtuyl
rubber has been observed to have some processing and fabrication problems such as
sticking to processing equipment during the milling and calendering operations.
[0005] Furthermore, it has sometimes been desired to provide a gum strip composition for
the innerliner which has both an enhanced building tack in its uncured state and a
good cured adhesion to the tire carcass while also having a satisfactory degree of
air impermeability.
[0006] Therefore, it is desired to provide a tire innerliner composition having enhanced
processing characteristics, uncured building tack and cured adhesion to a tire carcass.
Statement and Practice of the Invention
[0007] In accordance with this invention, a pneumatic rubber tire is provided having an
integral innerliner comprising a compounded rubber composition comprised of a sulfur
cured blend of 80 to 95 phr of at least one halobutyl rubber selected from chlorobutyl
rubber and bromobutyl rubber and 20 to 5 phr of at least one unsaturated copolymer
of propylene oxide and 2 to 10 weight percent based on the propylene oxide of at least
one copolymerizable monomer selected from butadiene monoxide, isoprene monoxide, 1,2-epoxy-3-allyloxypropane
(allyl glycidyl ether) and limonene monoxide. The preferred copolymerizable monomer
is allyl glycidyl ether.
[0008] In practice, the innerliner composition is first prepared as an uncured compounded
rubber gum strip, constructed as an inner surface (exposed inside surface) of an uncured
rubber tire structure, (carcass), and sulfur co-cured with the tire carcass during
the tire curing operation under conditions of heat and pressure. Thus, the innerliner
becomes an integral part of the tire by being co-cured therewith as compared to being
a simple adherent laminate.
[0009] The innerliner rubbers can be compounded with conventional rubber compounding ingredients
comprised of carbon black, zinc oxide, stearic acid, rubber processing oil, sulfur,
accelerator and antidegradant and then typically extruded and/or calendered to form
the uncured gum strip.
[0010] The preferred unsaturated polymer of alpha-olefin oxide is a copolymer of propylene
oxide and allyl glycidyl ether. Such copolymer and a method for its preparation is
disclosed in U.S. Patent 3,509,068.
[0011] An important feature of this invention is the discovery that the halobutyl rubber/alpha-olefin
oxide copolymer blend provides a sulfur curable tire innerliner composition which
has been observed to provide an improvement in its rubber compound processability
and uncured building tack and also its cured adhesion to a rubber tire carcass compound
as compared to a tire innerliner composition composed only of the halobutyl rubber
as its polymer component. Although the innerliner rubber blend composition has been
observed to exhibit an increase in air permeability as compared to the halobutyl rubber
innerliner composition, it is considered that the resultant air permeability of the
polymer blend is satisfactory, particularly in view of its observed enhanced processability.
[0012] The uncured tire carcass rubber interface with which the innerliner is sulfur co-cured
can be of various sulfur curable rubber and rubber blends such as, for example, polybutadiene,
polyisoprene and styrene/ butadiene copolymer rubbers.
[0013] Typically the innerliner has an uncured gum thickness in the range of about 0.03
to about 0.08 inch (0.08-0.2 cm), depending somewhat on the tire size, its intended
use and degrees of air retention desired.
[0014] The pneumatic tire with the integral innerliner composition may be constructed in
the form of a passenger tire, truck tire, or other type of bias or radial pneumatic
tire.
[0015] The practice of this invention is further illustrated by reference to the following
example which is intended to be representative rather than restrictive of the scope
of the invention as claimed. Unless otherwise indicated, all parts and percentages
are by weight.
Example 1
[0016] Several blend compositions of chlorobutyl rubber and copolymer of propylene oxide
and allyl glycidyl ether were prepared as a compounded rubber composition by mixing
in a size BR Banbury blender the chlorobutyl rubber and the copolymer as shown in
the following Table 1. Additional compounding ingredients comprised of carbon black,
zinc oxide, stearic acid, sulfur and accelerators were mixed with the blend as a two
step mixing process in which all of the ingredients were mixed in the first step except
for sulfur and accelerators which were added and mixed in the second step. The control
compound A is based on the chlorobutyl rubber and experimental compounds B-E are based
on the blend.

[0017] Properties of the cured innerliner composition are shown in Table 2 with Composition
A being a control as a chlorobutyl rubber and Compositions B-E being the experimental
compositions as the rubber blends. The compositions had been cured for about 36 minutes
at about 150°C.

[0018] The compounded rubber compositions were calendered into strips with fabric backing
having a thickness of 0.14 cm (0.055 inches) and 20.3 cm (8 inches) wide for preparation
of Ketjen tack and peel adhesion test samples and calendered into strips having a
thickness of 0.06 cm (0.022 inch) and 20.3 cm (8 inches) wide for air permeability
test samples prior to curing.
[0019] A comparison of cure behavior, stress strain properties (tensile and elongation),
tack and cured adhesion to other tire components, and air permeability has been shown
in Table 2.
[0020] Although the experimental blend compositions B-E exhibited a slower rate of cure
when compared to the control A, the stress strain properties of tensile and elongation
were observed to be comparable. The slower rate of cure of the blend compositions
B-E was not considered to be a serious consideration since the innerliner is in direct
contact with the hot cure bladder during the tire cure cycle.
[0021] All of the tested compounds were observed to exhibit excellent tack to themselves
and poorer tack to the representative chafer stock, whereas the experimental blend
compositions were observed to show improved tack to representative apex and carcass
stocks when compared to the control.
[0022] The cured adhesion of the test compounds to themselves or to representative apex
or chafer stocks cannot be directly or reasily compared on a numerical basis since
the failures occurred at the fabric backing instead of the stock interface. These
results indicate, however, that adequate adhesion should exist between these rubber
compounds. In the case of cured adhesion to the representative carcass stock, the
control test sample A exhibited adhesive failure at the interface between the cured
rubber compounds. In contrast, the blends containing 10 to 20 phr of the copolymer
exhibited higher values of cured adhesion, which were actually failures at the fabric
backing, and are therefore considered to have higher adhesion to the representative
carcass stock.
[0023] Although the experimental blends exhibited a steady increase of air permeability
relative to the control (1.1/
1 to 1.7/,) as the level of the copolymer in the blend is increased from 5 to 20 phr,
it is considered that the air permeability is within satisfactory limits. Indeed,
a natural rubber sample of the same thickness would be expected to demonstrate an
air permeability ratio of about 10/1 as compared to control sample A. Thus, even in
the worst case, the air permeability of sample E would be about 6 times less than
a comparable sample of natural rubber compound.
[0024] The processing of the samples B-E was noticeably improved over control sample A.
During the milling and calendering operation prior to testing, the blend compositions,
particularly at the 10 to 20 phr level of the copolymer in the blend, were observed
to be easier to process as a result of less sticking to a two roll breakdown mill
and the calender used to prepare the test samples. In particular, the control composition
A was found to be more difficult to remove from the roll mill (because of its sticking
to a roll) and also more difficult to calender as a gum strip (because of sticking
to a calender roll) than the experimental compositions B-E.
[0025] While certain representative embodiments and details have been shown for the purpose
of illustrating the invention, it will be apparent to those skilled in this art that
various changes and modifications may be made therein without departing from the scope
of the invention, as claimed.
1. Pneumatischer Reifen mit einer intergralen Innenauskleidung, dadurch gekennzeichnet,
daß sie eine compoudierte Kautschukmasse aufweist aus einer Schwefel-vulkanisierten
Mischung aus 80 bis 95 phr wenigstens eines Halogenbutylkautschuks, ausgewählt aus
Chlorbutylkautschuk und Brombutylkautschuk, und 20 bis 5 phr wenigstens eines ungesättigten
Copolymeren aus Propylenoxid und 2 bis 10 Gew.-%, bezogen auf das Propylenoxid, wenigstens
eines copolymerisierbaren Monomeren, ausgewählt aus Butadienmonoxid, Isoprenmonoxid,
1,2-Epoxy-3-allyloxypropan (Allylglycidylether) und Limonenmonoxid.
2. Pneumatischer Reifen mit einer integralen Innenauskleidung, dadurch gekennzeichnet,
daß sie eine compoundierte Kautschukmasse aufweist aus einer Schwefel-vulkanisierten
Mischung aus 80 bis 95 phr Chlorbutylkautschuk und 20 bis 5 phr eines ungesättigten
Copolymeren aus Proplenoxid und 2 bis 10Gew.- %, bezogen auf das Propylenoxid, eines
Allylglycidylethers.
1. Bandage pneumatique en caoutchouc muni d'un calandrage intérieur faisant partie
intégrante de celui-ci, caractérisé en ce que ce calandrage intérieur est constitué
d'une composition de caoutchouc composé comprenant un mélange vulcanisé constitué
de 80 à 95 parties en poids par cent parties en poids de caoutchouc d'au moins un
caoutchouc halobutyle choisi parmi le caoutchouc chlorobutyle et le caoutchouc bromobutyle,
de 20 à 5 parties en poids par cent parties en poids de caoutchouc d'au moins un copolymère
insaturé d'oxyde de propylène et de 2 à 10 pourcent en poids basé sur l'oxyde de propylène
d'au moins un monomère copolymérisable choisi parmi le monoxyde de butadiène, le monoxyde
d'isoprène, le 1,2-époxy-3-allyloxypropane (éther allylglycidylique) et le monoxyde
de limonène.
2. Bandage pneumatique en caoutchouc muni d'un calandrage intérieur faisant partie
intégrante de celui-ci, caractérisé en ce que ce calandrage intérieur est constitué
d'une composition de caoutchouc composé comprenant un mélange vulcanisé constitué
de 80 à 95 parties en poids par cent parties en poids de caoutchouc de caoutchouc
chlorobutyle, de 20 à 5 parties en poids par cent parties en poids de caoutchouc d'un
copolymère insaturé d'oxyde de propylène et de 2 à 10 pourcent en poids basé sur l'oxyde
de propylène d'éther allylglycidylique.